title: Effect of the carboxylate shift on the reactivity of zinc complexes in the gas phase.
abstract: The effect of different modes of the carboxylato ligands on the reactivity of gaseous zinc-acetate complexes is reported. Using infrared multiphoton dissociation spectroscopy, it is demonstrated that the coordination of acetate in [(Imi)(n)Zn(CH(3)COO)](+) complexes (Imi = imidazole, n = 1-3) changes from bi- to monodentate upon coordination of the third imidazole ligand. This so-called carboxylate shift substantially influences the reactivity of the zinc-acetate complexes in comparison to complexes with monodentate counterions. The differences in reactivities are demonstrated on the ligand exchange reactions of [L(n)ZnX](+) (n = 2 or 3,; L = imidazole or pyridine; X = OH, Cl, CH(3)COO, and CH(3)CONHO).
authors.affiliation: Department of Organic Chemistry, Charles University in Prague, Prague, Czech Republic.
authors.forename: Lucie
authors.initials: L
authors.lastname: Duchácková
authors.forename: Detlef
authors.initials: D
authors.lastname: Schröder
authors.forename: Jana
authors.initials: J
authors.lastname: Roithová
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005740:Gases / Q000737:chemistry; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D015032:Zinc / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D005740:Gases; D009942:Organometallic Compounds; D015032:Zinc